WO2019042951A1 - Procédé amélioré de phosphatation sans nickel de surfaces métalliques - Google Patents
Procédé amélioré de phosphatation sans nickel de surfaces métalliques Download PDFInfo
- Publication number
- WO2019042951A1 WO2019042951A1 PCT/EP2018/073056 EP2018073056W WO2019042951A1 WO 2019042951 A1 WO2019042951 A1 WO 2019042951A1 EP 2018073056 W EP2018073056 W EP 2018073056W WO 2019042951 A1 WO2019042951 A1 WO 2019042951A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- ions
- metallic surface
- water
- phosphating
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 title abstract description 25
- 239000002184 metal Substances 0.000 title abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 90
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 30
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 28
- 239000010452 phosphate Substances 0.000 claims abstract description 25
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 molybdenum ions Chemical class 0.000 claims description 33
- 238000004140 cleaning Methods 0.000 claims description 26
- 229910052750 molybdenum Inorganic materials 0.000 claims description 16
- 239000011733 molybdenum Substances 0.000 claims description 16
- 235000019353 potassium silicate Nutrition 0.000 claims description 13
- 239000008139 complexing agent Substances 0.000 claims description 12
- 239000003599 detergent Substances 0.000 claims description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims description 7
- 229940050410 gluconate Drugs 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004111 Potassium silicate Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 235000011180 diphosphates Nutrition 0.000 claims description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims 1
- 239000012459 cleaning agent Substances 0.000 abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 239000002253 acid Substances 0.000 description 25
- 235000021317 phosphate Nutrition 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 229910001868 water Inorganic materials 0.000 description 16
- 239000003973 paint Substances 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 229920002873 Polyethylenimine Polymers 0.000 description 8
- 238000005246 galvanizing Methods 0.000 description 8
- 229910000838 Al alloy Inorganic materials 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 229920000768 polyamine Polymers 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910001335 Galvanized steel Inorganic materials 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000008397 galvanized steel Substances 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000011135 tin Substances 0.000 description 4
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 4
- 229910000165 zinc phosphate Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 229920000123 polythiophene Polymers 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 239000012487 rinsing solution Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000004761 hexafluorosilicates Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
- C23C22/365—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and nickel cations
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/14—Silicates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/16—Phosphates including polyphosphates
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/36—Organic compounds containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
- C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/16—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions using inhibitors
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/16—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions using inhibitors
- C23G1/18—Organic inhibitors
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/16—Metals
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/20—Industrial or commercial equipment, e.g. reactors, tubes or engines
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/105—Nitrates; Nitrites
Definitions
- the present invention relates to a process for substantially nickel-free phosphating of a metallic surface using a specific detergent composition, this detergent composition itself and a process-phosphate-coated metallic surface and their use.
- Such phosphate coatings are mainly used in the automotive industry and the general industry.
- KTL cathodically deposited electrodeposition paints
- phosphate coatings are usually applied by means of a nickel-containing phosphating solution.
- the elementary or as alloying constituent, e.g. Zn / Ni, deposited nickel ensures a suitable conductivity of the coating in the subsequent electrodeposition coating.
- nickel ions are no longer desirable as part of treatment solutions because of their high toxicity and environmental toxicity, and should therefore be avoided or at least reduced in content as much as possible.
- the object of the present invention was therefore to provide a method with which metallic surfaces can be phosphated essentially nickel-free, wherein the aforementioned disadvantages of the prior art are avoided.
- a metallic surface is treated successively with the following compositions: i) with an alkaline aqueous cleaning composition containing at least one water-soluble silicate and then ii) with an acidic, aqueous, substantially nickel-free phosphating composition comprising zinc ions, manganese ions and phosphate ions.
- an uncoated metallic surface on the other hand, but also an already conversion coated metallic surface can be treated by the method according to the invention.
- an already conversion-coated metallic surface should therefore always be included as well, however, it is preferably an uncoated metallic surface.
- aqueous composition refers to a composition which contains water as solvent / dispersion medium at least in part, preferably for the most part, ie more than 50% by weight It may therefore be, for example, an emulsion, but it is preferably a solution, ie a composition which contains no coarsely dispersed constituents.
- a silicate is meant that at 25 ° C, a water solubility (in deionized water) of at least 1 mg / l, preferably at least 10 mg / l, more preferably at least 100 mg / l, more preferably at least 1 g / l, more preferably at least 10 g / l, even more preferably at least 100 g / l, more preferably at least 200 g / l, more preferably at least 300 g / l and more preferably at least 350 g / l.
- the silicate can also be present as a colloidal solution.
- a composition contains less than 0.3 g / l of nickel ions, it should be considered as "essentially nickel-free" for the purposes of the present invention.
- the phosphating composition preferably contains less than 0.1 g / l and more preferably less than 0.01 g / l
- phosphate ions also means hydrogen phosphate, dihydrogen phosphate and phosphoric acid.
- pyrophosphoric acid and polyphosphoric acid as well as all their partially and completely deprotonated forms should be included.
- metal ion is understood as meaning either a metal cation, a complex metal cation or a complex metal anion.
- the metallic surface is preferably steel, a steel alloy, a hot-dip galvanizing, an electrolytic galvanizing, a zinc alloy such as Zn / Fe or Zn / Mg, aluminum or an aluminum alloy.
- the hot-dip galvanizing and the electrolytic galvanizing in each case are in particular such on steel.
- the metallic surface is at least partially galvanized.
- the inventive method is particularly suitable for multi-metal applications, in particular for metallic surfaces, which in addition to a galvanizing on steel, preferably a hot dip galvanizing and an electrolytic galvanizing, aluminum and / or an aluminum alloy, preferably an aluminum alloy.
- the metallic surface is, according to the invention, first cleaned (step i), in particular degreased, in an alkaline, aqueous cleaning composition.
- an acidic or neutral pickling composition may also be used for this purpose.
- the detergent composition may be obtained from a concentrate by dilution with a suitable solvent, preferably with water, preferably by a factor between 1.5 and 1000, more preferably between 50 and 200, and if necessary adding a pH modifying substance.
- the at least one water-soluble silicate contained in the detergent composition causes a better cleaning action and reduces the pickling attack in the cleaning bath (inhibiting effect).
- the at least one water-soluble silicate in this case preferably comprises at least one water glass, in particular a lithium water glass, a soda water glass and / or a potassium silicate, more preferably a soda water glass and / or a potassium silicate, and / or at least one metasilicate such as disodium metasilicate (Na 2 SiO 3).
- the at least one water-soluble silicate comprises a soda water glass or a potassium silicate glass.
- the soda water glass is preferably one having a molar Na 2 O: SiO 2 ratio in the range from 1 to 4.
- the potassium silicate glass is likewise preferably one having a molar K 2 O: SiO 2 ratio in the range from 1 to 4 ,
- the at least one water-soluble silicate is preferably present in a total concentration in the range from 0.01 to 15 g / l, more preferably from 0.2 to 13 g / l and particularly preferably from 0.5 to 10 g / l.
- the detergent composition may contain, in addition to the at least one water-soluble silicate, at least one cationic, nonionic and / or anionic surfactant and / or other additives, in particular complexing agents, oxidizing agents, oils and / or auxiliaries, e.g. Solvent, borate and / or carbonate included.
- at least one water-soluble silicate at least one cationic, nonionic and / or anionic surfactant and / or other additives, in particular complexing agents, oxidizing agents, oils and / or auxiliaries, e.g. Solvent, borate and / or carbonate included.
- complexing agents cause a complexation of water hardness and dissolved cations, which by the pickling attack in the cleaner bath go into solution or present.
- Preferred complexing agents are on the one hand phosphorus-containing complexing agent.
- phosphate-based complexing agents preferably in turn condensed phosphates such as e.g. Pyrophosphates, tripolyphosphates and other polyphosphates - as well as phosphonic acids, e.g. 1-Hydroxyethane- (1, 1-diphosphonic acid) (HEDP) and its salts.
- condensed phosphates such as e.g. Pyrophosphates, tripolyphosphates and other polyphosphates - as well as phosphonic acids, e.g. 1-Hydroxyethane- (1, 1-diphosphonic acid) (HEDP) and its salts.
- HEDP 1-Hydroxyethane- (1, 1-diphosphonic acid)
- the phosphorus-containing, in particular the phosphate-based complexing agents are preferably in a total concentration in the range of 0.01 to 15 g / l, more preferably from 0.05 to 13 g / l and particularly preferably from 0.1 to 10 g / l (calculated as Tetrapotassium pyrophosphate).
- preferred complexing agents are hydroxycarboxylic acids which have at least one hydroxyl group and at least one carboxyl group, and their salts, in particular sugar acids and their salts, particularly preferably heptonate and gluconate. Very particular preference is given to gluconate.
- Such complexing agents are preferably present in a total concentration in the range of from 0.01 to 6 g / l, more preferably from 0.05 to 5 g / l, and most preferably from 0.1 to 4 g / l (calculated as sodium gluconate).
- the cleaning composition contains at least one phosphorus-containing complexing agent, in particular a pyrophosphate and / or a tripolyphosphate, and at least one hydroxycarboxylic acid or its salt, in particular gluconate.
- phosphorus-containing complexing agent in particular a pyrophosphate and / or a tripolyphosphate
- hydroxycarboxylic acid or its salt in particular gluconate.
- Very particularly preferred combinations are: i) tetrapotassium pyrophosphate and gluconate,
- a preferred oxidizing agent is nitrite.
- the oxidizing agents are preferably in a total concentration in the range of 10 to 100 mg / l, more preferably from 20 to 50 mg / l (calculated as nitrite) before.
- the cleaner composition is preferably added no iron ions, in particular no iron (III) ions. If necessary, iron ions present in the cleaning bath originate in this case exclusively from the treated metallic Surface.
- the pH of the cleaner composition is preferably in the range of 9.5 to 13, in particular in the range of 10.5 to 12, more preferably in the range of 10.7 to 12.0, more preferably of 1 1, 0 to 12, 0, more preferably from 1 1, 3 to 12.0 and particularly preferably in the range of 1 1, 5 to 12.0.
- the detergent composition preferably has a temperature in the range of from 35 to 70, more preferably from 40 to 65, and most preferably from 45 to 60 ° C.
- the treatment of the metallic surface with the detergent composition is preferably carried out for 30 to 600, more preferably for 60 to 480 and most preferably for 90 to 360 seconds, preferably by means of dipping or spraying, or the combination of both.
- the metallic surface is first sprayed with the detergent composition for 30 to 90 seconds and then immersed in it for 100 to 300 seconds.
- the cleaning / pickling and before the treatment of the metallic surface with the phosphating composition takes place advantageously at least one rinsing of the metallic surface with water, wherein the water optionally also dissolved in water additive such.
- water additive such as a nitrite or surfactant may be added.
- the activation composition serves to deposit a plurality of ultrafine phosphate particles as seed crystals on the metallic surface. These help in the subsequent process step, in contact with the phosphating - preferably without interim rinsing - form a particular crystalline phosphate layer with the highest possible number of densely arranged fine phosphate crystals or a substantially closed phosphate layer.
- alkaline compositions based on titanium phosphate or zinc phosphate are suitable as activating compositions.
- activating agents in particular titanium phosphate or zinc phosphate, already to the cleaner composition, ie to carry out purification and activation in one step.
- the acidic, aqueous, substantially nickel-free phosphating composition includes zinc ions, manganese ions, and phosphate ions.
- the phosphating composition may be obtained from a concentrate by dilution with a suitable solvent, preferably with water, by a factor between 1.5 and 100, preferably between 5 and 50, and if necessary adding a pH modifying substance.
- the phosphating composition preferably comprises the following components in the following preferred and particularly preferred concentration ranges:
- a concentration in the range from 0.3 to 2.5 g / l has already been found to be advantageous with regard to the free fluoride, a concentration in the range from 10 to 250 mg / l.
- the complex fluoride is preferably tetrafluoroborate (BF 4 _ ) and / or hexafluorosilicate (SiF 6 2 ⁇ ).
- Al 3+ is a bad poison in phosphating systems and can be removed from the system by complexation with fluoride, eg as cryolite.
- fluoride eg as cryolite.
- Complex fluorides become the bath fluoride also helps to improve paint adhesion and corrosion protection, and complex fluoride on galvanized material helps to prevent defects such as sticking ,
- the phosphating composition has a content of iron (III) ions.
- the iron (III) ions are preferably added to the phosphating composition.
- an addition amount of iron (III) ions in the range from 0.001 to 0.2 g / l, more preferably from 0.001 to 0.1 g / l, more preferably from 0.005 to 0.1 g / l, particularly preferably from 0.005 to 0.05 g / l and most preferably from 0.005 to 0.02 g / l.
- the phosphating composition preferably contains at least one accelerator selected from the group consisting of the following compounds in the following preferred and particularly preferred concentration ranges:
- the at least one accelerator is H2O2.
- the phosphating composition preferably contains less than 1 g / l, more preferably less than 0.5 g / l, more preferably less than 0.2 g / l and most preferably less than 0.1 g / l of nitrate.
- the nitrate in the phosphating causes an additional acceleration of Stratification reaction, which leads to lower coating weights but mainly reduces the incorporation of manganese in the crystal.
- the manganese content of the phosphate coating is too low, this is at the expense of its alkali resistance.
- Alkali resistance in turn plays a crucial role in subsequent cathodic electrodeposition.
- an electrolytic splitting of water occurs at the substrate surface: Hydroxide ions are formed. This causes the pH at the interface of the substrate to increase. It is true that only then can the electrocoating be agglomerated and separated. However, the increased pH can also damage the crystalline phosphate layer.
- the phosphating composition preferably has a temperature in the range of 30 to 55 ° C.
- the phosphating composition can be characterized by the following preferred and particularly preferred parameter ranges:
- FS stands for free acid
- FS (verd.) For free acid (diluted)
- GSF for total acid according to Fischer
- GS for total acid
- S value for acid value
- a suitable vessel for example a 300 ml Erlenmeyer flask. If the phosphating composition contains complex fluorides, 2-3 g of potassium chloride are added to the sample. Then, using a pH meter and an electrode, it is titrated with 0.1 M NaOH to a pH of 3.6. The amount of 0.1 M NaOH consumed in ml per 10 ml of the phosphating composition gives the value of the free acid (FS) in points.
- the free acid (diluted) 10 ml of the phosphating composition are pipetted into a suitable vessel, for example into a 300 ml Erlenmeyer flask. Subsequently, 150 ml of deionized water are added. Using a pH meter and an electrode, titrate with 0.1 M NaOH to a pH of 4.7. The consumed amount of 0.1 M NaOH in ml per 10 ml of the diluted phosphating composition gives the value of the free acid (diluted) (FS (dil.)) In points. About the difference to the free acid (FS) the content of complex fluoride can be determined. If this difference is multiplied by a factor of 0.36, the content of complex fluoride is SiF6 2 ⁇ in g / l.
- the dilute phosphating composition is titrated to pH 8.9 after addition of potassium oxalate solution using a pH meter and electrode with 0.1 M NaOH.
- the consumption of 0.1 M NaOH in ml per 10 ml of the diluted phosphating composition hereby gives the total Fischer acid (GSF) in points. If this value is multiplied by 0.71, the total content of phosphate ions is calculated as P2O5.
- the total acid (GS) is the sum of the divalent cations present as well as free and bound phosphoric acids (the latter being phosphates). It is determined by the consumption of 0.1 M NaOH using a pH meter and an electrode. For this purpose, 10 ml of the phosphating composition are pipetted into a suitable vessel, for example a 300 ml Erlenmeyer flask and diluted with 25 ml of deionized water. It is then titrated with 0.1 M NaOH to a pH of 9. The consumption in ml per 10 ml of the diluted phosphating composition corresponds to the total acid score (GS).
- S value stands for the ratio FS: GSF and is given by Divide the value of the free acid (FS) by the value of the total acid according to Fischer (GSF).
- a temperature of the phosphating of less than 45 ° C, preferably in the range between 35 and 45 ° C leads to further improved corrosion and paint adhesion values.
- the treatment of the metallic surface with the phosphating composition is preferably carried out for 30 to 480, particularly preferably for 60 to 300 and very particularly preferably for 90 to 240 seconds, preferably by means of dipping or spraying.
- the metallic surface is rinsed after treatment with the phosphating composition, more preferably rinsed with demineralized water or city water.
- the already treated with the phosphating, ie phosphate-coated, metallic surface is still treated with an aqueous Nach Whyzusammen experience.
- the metallic surface is optionally dried before treatment with the Nach Whyzusammen experience.
- the rinse-off composition can be obtained from a concentrate by dilution with a suitable solvent, preferably with water, by a factor between 1.5 and 1000, preferably between 5 and 700, and if necessary adding a pH modifying substance.
- the treatment with the post-rinse composition makes it possible to adjust the electrical conductivity of the phosphate-coated metal surface in a targeted manner by producing defined pores in the phosphate layer.
- the conductivity may be either greater than, equal to, or smaller than that of a corresponding metal surface provided with a nickel-containing phosphate coating.
- the adjusted electrical conductivity of the phosphate-coated metal surface can be influenced by varying the concentration of a given metal ion or polymer in the post-rinse composition.
- the post-rinse composition contains at least one kind of metal ion selected from the group consisting of the ions of the following metals in the following preferred, most preferred and most preferred concentration ranges (all calculated as corresponding metal): Mo 1 to 500 mg / l 10 to 250 mg / l 20 to 150 mg / l
- the metal ions contained in the post-rinse composition are deposited either in the form of a salt which preferably contains the corresponding metal cation (eg molybdenum or tin) in at least two oxidation states - in particular in the form of an oxide hydroxide, a hydroxide, a spinel or a defect spinel - or elementally on the surface to be treated (eg copper, silver, gold or palladium).
- a salt which preferably contains the corresponding metal cation (eg molybdenum or tin) in at least two oxidation states - in particular in the form of an oxide hydroxide, a hydroxide, a spinel or a defect spinel - or elementally on the surface to be treated (eg copper, silver, gold or palladium).
- the metal ions are molybdenum ions. These are preferably added as molybdate, more preferably as ammonium heptamolybdate and more preferably as ammonium heptamolybdate x 7 H2O to the post-rinse composition.
- the molybdenum ions can also be added as sodium molybdate.
- molybdenum ions may also be added to the post-rinse composition in the form of at least one molybdenum cation-containing salt, such as molybdenum chloride, and then oxidized to molybdate by a suitable oxidizing agent, for example by the accelerators described above.
- a suitable oxidizing agent for example by the accelerators described above.
- the post-rinse composition itself contains a corresponding oxidizing agent.
- the post-rinse composition contains molybdenum ions in combination with copper ions, tin ions or zirconium ions.
- molybdenum ions in combination with zirconium ions and optionally a polymer or copolymer, in particular selected from Group consisting of the polymer classes of polyamines, polyethyleneamines, polyanilines, polyimines, polyethylenimines, polythiophenes and polypryrenes and mixtures and copolymers thereof and polyacrylic acid, wherein the content of molybdenum ions and zirconium ions is in each case in the range from 10 to 500 mg / l (calculated as metal) ,
- the content of molybdenum ions is preferably in the range from 20 to 150 mg / l, particularly preferably from 25 to 100 mg / l and very particularly preferably from 30 to 75 mg / l and the content of zirconium ions in the range from 50 to 300 mg / l, more preferably from 50 to 150 mg / l.
- the metal ions are copper ions.
- the rinsing solution then contains these in a concentration of 100 to 500 mg / l, more preferably from 150 to 225 mg / l.
- the rinse-off composition according to the invention comprises at least one polymer selected from the group consisting of the polymer classes of the polyamines, polyethyleneamines, polyanilines, polyimines, polyethyleneimines, polythiophenes and polypryrenes and also their mixtures and copolymers.
- the at least one polymer is preferably in a concentration in the range of 0.1 to 5 g / l, more preferably from 0.1 to 3 g / l, more preferably from 0.3 to 2 g / l and particularly preferably in the range from 0.5 to 1.5 g / l (calculated as pure polymer).
- the polymers used are preferably cationic polymers, in particular polyamines, polyethyleneamines, polyimines and / or polyethyleneimines. Particular preference is given to using a polyamine and / or polyimine, very particularly preferably a polyamine.
- the rinse-off composition according to the invention comprises at least one kind of metal ion selected from the group consisting of the ions of molybdenum, copper, silver, gold, palladium, tin, antimony, titanium, zirconium and hafnium and at least one polymer selected from the group consisting of the polymer classes of polyamines, polyethyleneamines, polyanilines, polyimines, polyethyleneimines, polythiophenes and polypryrenes and their Mixtures and copolymers, in each case in the following preferred, particularly preferred and very particularly preferred concentration ranges (polymer calculated as pure polymer and metal ions calculated as the corresponding metal).
- metal ion selected from the group consisting of the ions of molybdenum, copper, silver, gold, palladium, tin, antimony, titanium, zirconium and hafnium
- polymer selected from the group consisting of the polymer classes of polyamines, polyethyleneamines, polyanilines, polyimines, polyethyleneimines, polythi
- the at least one polymer is a cationic polymer, in particular a polyamine and / or polyimine, and the metal ions are copper ions, molybdenum ions and / or zirconium ions, in each case in the following preferred, particularly preferred and very particular preferred concentration ranges (polymer calculated as pure polymer and metal ions calculated as the corresponding metal).
- the post-rinse composition comprises, in particular, when the metallic surface is aluminum or an aluminum alloy, preferably additionally 20 to 500 mg / l, more preferably 50 to 300 mg / l and particularly preferably 50 to 150 mg / l of Ti, Zr and / or Hf in complexed form (calculated as metal). These are preferably fluoro complexes.
- the post-rinse composition preferably comprises 10 to 500 mg / l, more preferably 15 to 100 mg / l, and most preferably 15 to 50 mg / l of free fluoride.
- the post-rinse composition contains Zr in complexed form (calculated as metal) and at least one kind of metal ions selected from the group consisting of the ions of molybdenum, copper, silver, gold, palladium, tin and antimony, preferably molybdenum.
- the pH of the post-rinse composition is preferably in the acidic range, more preferably in the range of 3 to 5, particularly preferably in the range of 3.5 to 5.
- the pH is preferably 3.5 to 4.5, and more preferably 3.5 to 4.0.
- the post-rinse composition is essentially nickel free. It preferably contains less than 0.1 g / l and more preferably less than 0.01 g / l of nickel ions.
- the post-rinse composition preferably has a temperature in the range of 15 to 40 ° C.
- the treatment of the metallic surface with the post-rinse composition is preferably carried out for 10 to 180, particularly preferably for 20 to 150 and very particularly preferably for 30 to 120 seconds, preferably by means of dipping or spraying.
- the metallic surface is first rinsed after the treatment with the Nach Whyzusammen GmbH, preferably with deionized water, and optionally dried.
- the present invention further relates to the alkaline aqueous cleaning composition described above, which contains at least one water-soluble silicate, as well as to the correspondingly described concentrate from which this cleaning composition is obtainable.
- the invention additionally relates to a phosphate-coated metallic surface obtainable by the process according to the invention.
- the invention still relates to the use of the coated with the inventive method metallic surfaces in the field of automotive, automotive suppliers or general industry.
- cleaning bath A By mixing the components in demineralized water, optionally adjusting the pH with phosphoric acid (cleaning bath A) and then diluting the mixture by a factor of 50 to 70, the following cleaning baths were prepared:
- the cleaning bath F and the cleaning bath G were also used.
- the cleaning bath F was identical to the cleaning bath B except for the pH of 10.5
- the cleaning bath G was identical to the cleaning bath E except for the pH of 10.5.
- the pH was adjusted both in the cleaning bath F and G with phosphoric acid.
- Hot dip galvanized steel (EA), electrolytically galvanized steel (G) and aluminum alloy AA 6014 (AI) test plates were immersed in one of the cleaning baths A to D at 60 ° C for 300 seconds and then in an activating bath at 25 ° C for 30 seconds containing 0.6 g / l zinc phosphate.
- the test panels were then immersed for 180 seconds at 45 ° C in one of the phosphating baths A ' to C and then for 30 seconds at 25 ° C in the rinse described above. After thorough rinsing with demineralized water, the test panels were also coated with a cathodic electrodeposition paint and a standard auto paint finish (filler, basecoat, clearcoat).
- test plates made of electrolytically as well as hot-dip galvanized steel were subjected to a VDA test (VDA 621-415, 10 rounds), whereby the undercoat (U) was determined in mm and the lacquer removal after rockfall (DIN EN ISO 20567-1, Verf. C) was determined.
- U undercoat
- DIN EN ISO 20567-1, Verf. C lacquer removal after rockfall
- the lattice cutting results of Table 1 clearly show the deterioration of the paint adhesion in nickel-free versus nickel-containing phosphating on hot-dip galvanized and electrolytically galvanized steel (compare VB2 vs. VB1, VB4 vs. VB3).
- VB2 vs. VB1, VB4 vs. VB3 By using a cleaning bath according to the invention, it is possible to achieve a paint adhesion in the nickel-free variant which almost corresponds to that of the nickel-containing variant (compare B1 vs. VB1 and B2 vs. VB3).
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- Chemical & Material Sciences (AREA)
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- Mechanical Engineering (AREA)
- Metallurgy (AREA)
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- Life Sciences & Earth Sciences (AREA)
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Abstract
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112020002882-7A BR112020002882A2 (pt) | 2017-08-31 | 2018-08-28 | método para fosfatização substancialmente isenta de níquel de uma superfície metálica, composição de limpeza alcalina e aquosa, concentrado, superfície metálica revestida com fosfato, e, uso da superfície metálica |
EP18756454.7A EP3676419B1 (fr) | 2017-08-31 | 2018-08-28 | Procédé amélioré de phosphatage sans nickel des surfaces métalliques |
US16/640,581 US11643731B2 (en) | 2017-08-31 | 2018-08-28 | Method for nickel-free phosphating metal surfaces |
MX2020002343A MX2020002343A (es) | 2017-08-31 | 2018-08-28 | Metodo mejorado para superficies metalicas fosfatadas sin niquel. |
JP2020512581A JP7279019B2 (ja) | 2017-08-31 | 2018-08-28 | 金属表面をニッケル非含有でリン酸塩処理するための改善された方法 |
CN201880056072.4A CN111065761A (zh) | 2017-08-31 | 2018-08-28 | 用于无镍磷化金属表面的改进方法 |
RU2020111711A RU2782710C2 (ru) | 2017-08-31 | 2018-08-28 | Улучшенный способ безникелевого фосфатирования металлических поверхностей |
ES18756454T ES2966844T3 (es) | 2017-08-31 | 2018-08-28 | Procedimiento mejorado para él fosfatado sin níquel de superficies metálicas |
KR1020207005575A KR20200045487A (ko) | 2017-08-31 | 2018-08-28 | 금속 표면을 니켈-무함유 인산염처리하는 개선된 방법 |
Applications Claiming Priority (2)
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EP17188783 | 2017-08-31 | ||
EP17188783.9 | 2017-08-31 |
Publications (1)
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WO2019042951A1 true WO2019042951A1 (fr) | 2019-03-07 |
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PCT/EP2018/073056 WO2019042951A1 (fr) | 2017-08-31 | 2018-08-28 | Procédé amélioré de phosphatation sans nickel de surfaces métalliques |
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Country | Link |
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US (1) | US11643731B2 (fr) |
EP (1) | EP3676419B1 (fr) |
JP (1) | JP7279019B2 (fr) |
KR (1) | KR20200045487A (fr) |
CN (1) | CN111065761A (fr) |
BR (1) | BR112020002882A2 (fr) |
ES (1) | ES2966844T3 (fr) |
MX (1) | MX2020002343A (fr) |
WO (1) | WO2019042951A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023046952A1 (fr) | 2021-09-27 | 2023-03-30 | Chemetall Gmbh | Composition aqueuse exempte de borate pour le nettoyage et le traitement de substrats métalliques |
Families Citing this family (1)
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WO2019042951A1 (fr) * | 2017-08-31 | 2019-03-07 | Chemetall Gmbh | Procédé amélioré de phosphatation sans nickel de surfaces métalliques |
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- 2018-08-28 BR BR112020002882-7A patent/BR112020002882A2/pt active Search and Examination
- 2018-08-28 KR KR1020207005575A patent/KR20200045487A/ko not_active Application Discontinuation
- 2018-08-28 CN CN201880056072.4A patent/CN111065761A/zh active Pending
- 2018-08-28 MX MX2020002343A patent/MX2020002343A/es unknown
- 2018-08-28 EP EP18756454.7A patent/EP3676419B1/fr active Active
- 2018-08-28 US US16/640,581 patent/US11643731B2/en active Active
- 2018-08-28 JP JP2020512581A patent/JP7279019B2/ja active Active
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023046952A1 (fr) | 2021-09-27 | 2023-03-30 | Chemetall Gmbh | Composition aqueuse exempte de borate pour le nettoyage et le traitement de substrats métalliques |
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KR20200045487A (ko) | 2020-05-04 |
JP7279019B2 (ja) | 2023-05-22 |
RU2020111711A (ru) | 2021-09-30 |
JP2021501829A (ja) | 2021-01-21 |
ES2966844T3 (es) | 2024-04-24 |
EP3676419A1 (fr) | 2020-07-08 |
US11643731B2 (en) | 2023-05-09 |
MX2020002343A (es) | 2020-07-13 |
EP3676419B1 (fr) | 2023-10-11 |
BR112020002882A2 (pt) | 2020-10-06 |
RU2020111711A3 (fr) | 2022-02-02 |
US20200199758A1 (en) | 2020-06-25 |
CN111065761A (zh) | 2020-04-24 |
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